U.S. patent number 3,925,315 [Application Number 05/507,836] was granted by the patent office on 1975-12-09 for diglycidyl ether of 4-methylol resorcinol.
This patent grant is currently assigned to The United States of America as represented by the Secretary of the Army. Invention is credited to John J. Schmid.
United States Patent |
3,925,315 |
Schmid |
December 9, 1975 |
Diglycidyl ether of 4-methylol resorcinol
Abstract
High yields of rapid curing epoxy resins derived from
1,3-diphenols and hng the formula: ##SPC1## Where m and n each have
values of at least 1. These resins can be cured at room temperature
and can be used for a variety of industrial applications including
adhesives, protective coatings and/or encapsulants for
heat-sensitive electrical components used, for example, in the
manufacture of fuzes.
Inventors: |
Schmid; John J. (Panama City,
FL) |
Assignee: |
The United States of America as
represented by the Secretary of the Army (Washington,
DC)
|
Family
ID: |
24020336 |
Appl.
No.: |
05/507,836 |
Filed: |
September 20, 1974 |
Current U.S.
Class: |
528/87; 523/458;
523/466; 549/554; 523/457; 523/459; 528/123; 549/555 |
Current CPC
Class: |
C08G
59/245 (20130101) |
Current International
Class: |
C08G
59/24 (20060101); C08G 59/00 (20060101); C08G
030/14 () |
Field of
Search: |
;260/348R,47,54 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Czaja; Donald E.
Assistant Examiner: Pertilla; T.
Attorney, Agent or Firm: Edelberg; Nathan Gibson; Robert P.
Elbaum; Saul
Government Interests
The invention described herein may be manufactured, used and
licensed by or for the United States Government for governmental
purposes without the payment to me of any royalty thereon.
Claims
What is claimed is:
1. A curable epoxy composition comprising an epoxy compound of the
formula: ##SPC13##
wherein m and n each have a value of at least 1, and a known
epoxide curing agent.
2. The composition of claim 1 wherein m and n each have a value of
1.
3. The composition of claim 2 wherein said curing agent is
diethylenetriamine.
4. A cured epoxy resin formed by mixing a compound of the formula:
##SPC14##
wherein m and n each have values of at least 1, and a catalytic
amount of a known epoxy curing agent.
5. The resin of claim 4 wherein m and n each have a value of 1.
6. The resin of claim 5 wherein said curing agent is
diethylenetriamine.
Description
BRIEF SUMMARY OF THE INVENTION
This invention relates to derivatives of 4-methylol resorcinol of
the formula: ##SPC2##
Wherein both m and n each have values of at least 1, and to curable
compositions and cured products based thereon. More particularly,
this invention relates to diglycidyl ethers of 4-methylol
resorcinol which can be rapidly cured at room temperature to form
high yields of the cured product which can be used for a variety of
industrial applications including adhesives, protective coatings
and/or encapsulants for heat-sensitive electrical components used,
for example, in the manufacture of fuzes.
BACKGROUND OF THE INVENTION
Epoxy resins have been extensively employed in various industrial
applications as potting agents, encapsulants, adhesives and
protective coatings, particularly in the production of fuzes. They
exhibit high mechanical strength and good electrical insulating
ability thus making them ideal for protecting delicate electronic
components. However, most resin systems have been found to cure
very slowly or incompletely at room temperature, resulting in
relatively long production times. Elevated temperatures are
frequently required for rapid and complete cures but such elevated
temperatures cannot be used where heat-sensitive electronic
components are being employed. The curing agents available for low
temperature rapid cures (i.e., Lewis acids) result in the formation
of a cured product having undesirable physical properties. The use
of a hardener to cure the resin rapidly, also usually results in
the impairment of some desirable physical property of the resin.
For example, a system cured with one of the available curing agents
or hardeners often results in the formation of an epoxy resin which
is too brittle, has a low chemical resistance and/or high rate of
shrinkage. Since the rapid curing of epoxy resin systems at ambient
temperatures is usually a function of the curing agent or hardener
and not of the resin activity, the properties of the fast curing
systems are limited by the curing agent or hardener employed.
If an epoxy resin could be modified to enhance reactivity toward a
relatively slow reacting curing agent, a much greater flexibility
in the formulating of epoxy resin systems would be available. Thus,
there has been a great need for a rapid-curing epoxy resin which
can be cured rapidly at room temperatures and which avoids many of
the drawbacks of the epoxy resins used heretofore. Such a resin
would have a wide variety of industrial applications including its
use as an adhesive for the rapid bonding of small heat-sensitive
electrical components.
OBJECTS OF THE INVENTION
Specifically, it is the primary object of the invention to provide
a highly reactive epoxy prepolymer which can be rapidly cured at
room temperature to form a cured product that can be used for a
variety of industrial applications.
Consistent with this primary object, it is a further object hereof
to provide rapidly cured epoxy resins that can be employed as
potting agents, encapsulants, adhesives and protective coatings for
delicate electronic components.
Still another, more important object of this invention is to
provide a highly reactive prepolymer having a sufficiently low
viscosity to enable incorporation of inert fillers in an amount
sufficient to control the exothermic temperature inherent in curing
said prepolymer.
A further object of this invention is to provide a rapidly curable
epoxy resin wherein the rate of cure is due to the reacitvity of
the prepolymer rather than the curing agent.
A still further object of this invention is to provide a rapidly
curing epoxy resin which can be produced in high yields by means of
a simple and efficient process that is amenable to large scale
production.
The invention will be better understood and objects other than
those set forth above will become apparent after reading the
following detailed description of preferred, yet illustrative,
embodiments hereof.
DETAILED DESCRIPTION OF THE INVENTION
It has now been discovered that these and other objects may be
accomplished by employing a novel prepolymer of the formula:
##SPC3##
wherein both m and n have values of at least 1, and wherein the
rapid curing is a function of the prepolymer rather than the curing
agent employed.
The compound of this invention possesses a hydroxyl group proximate
to the epoxy groups to enhance the reactivity of the epoxide rings,
both intramolecularly and intermolecularly. The hydroxyl group
exerts an anchimeric increase in the rate of the epoxide ring
opening thereby accelerating the rate of cure through hydrogen
bonding with the oxygen of the epoxide ring.
While it is possible for both m and n to have values greater than
1, it should be pointed out that best results are obtained when
both m and n each are equal to 1. When m and n are each greater
than 1, the rate of cure of the resin will decrease somewhat.
Likewise, the substitution of an ethylol or propylol group for the
methylol group will also cause the rate of cure to be decreased
somewhat.
Preparation of compounds falling within the scope of the above
formula is conveniently accomplished by a three-step, high-yield
sequence starting with resorcinol. The synthesis of the resin
monomer is as follows: ##SPC4##
Intermediate compound II, .beta.-resorcyladehyde, is prepared from
the resorcinol starting material I by a modified Gatterman
reaction. Carefully controlled condensation of this material with
epichlorohydrin results in the formation of the ether intermediate
III. Subsequent conversion to the final product may be attained by
either borohydride reduction or catalytic hydrogenation.
A particularly preferred resin monomer used in the practice of this
invention is the diglycidyl ether of 4-methylol resorcinol. This
compound is prepared by first formylating the resorcinol by means
of a modified Gatterman reaction. See Adams, R., and Levine, I., J.
Am. Chem. Soc., 45, 2373 (1923).
In a 500-ml. three-neck round-bottom flask fitted with a mechanical
stirrer, gas "sparge," and condenser, were placed 20 grams (0.18
mole) of resorcinol I, 27.2 grams (0.55 mole) of sodium cyanide,
200 ml. of anhydrous chloroform and 25 ml. of anhydrous ether. Dry
HCl gas was bubbled into the solution with stirring for 1.5 hours
until the reaction mixture turned pink and a gummy solid settled to
the bottom of the flask. The residual hydrogen cyanide produced was
destroyed by passing it through a 25 percent aqueous sulfuric acid
trap and then a 25 percent aqueous sodium hydroxide trap. The
solvent was decanted and the residue was dissolved in 100 ml. of
water and boiled for 5 minutes. After cooling the resultant
solution to room temperature, 12.4 grams of crude
.beta.-resorcylaldehyde (II) were collected by filtration. The
mother liquid was allowed to stand overnight at room temperature
and another 10.7 grams of product was obtained, giving a combined
23.1 grams (95 percent) of crude .beta.-resorcylaldehyde (II).
Crude II was then decolorized with activated charcoal and
recrystallized from water to yield an off-white solid, melting
point of 134.degree. - 135.degree. C. (lit, 135.degree. -
136.degree. C.); IR, 1650 cm..sup.-.sup.1 (--CHO), 3500 - 3700
cm..sup.-.sup.1 (--OH). This reaction is depicted as follows:
##SPC5##
The diglycidyl ether of .beta.-resorcylaldehyde (III) was obtained
by condensing II with epichlorohydrin in the presence of a base.
##SPC6##
In a 1-l. three-neck round-bottom flask equipped with a mechanical
stirrer, a Dean-Stark trap, and a condenser, were placed 30 grams
(0.22 mole) of II and 420 grams (5 mole) of epicholorohydrin. To
this mixture, held at reflux, was added dropwise over a period of 3
hours a solution of 18 grams (0.45 mole) of sodium hydroxide in 27
ml. of water. The reaction mixture was then refluxed an additional
2.5 hours until 34.5 ml. (theoretical yield 34.8 ml.) of water had
been collected in the Dean-Stark trap. Sodium chloride and a small
amount of bright orange solid polymeric material were removed by
filtration. The solvent was removed in vacuo to yield 53.6 grams of
III as a yellow oil (viscosity 9 stokes) which slowly crystallized
upon standing. Analytical thin layer chromatography revealed the
crude product to be predominantly III (90 percent) along with a
small amount of less soluble, more polar material (presumably
higher homologs of resin III since no starting material was
present). Pure III could be obtained by recrystallization from
acetone or methanol, M.P. 74.degree. - 77.degree. C; IR, 910
cm..sup.-.sup.1 (epoxide) 1675 cm..sup.-.sup.1 (CHO); NMR,
.tau.CDCl.sub.3 7.2 - 7 m. (4H), 6.8 - 6.5 m. (2H), 6.2 - 5.5 m.
(4H), 3.4 m. (2H), 2.2 d. (2H), 0.5 d. (1H).
The intermediate III could be converted to the diglycidyl ether of
4-methylol resorcinol IV by either (A) catalytic hydrogenation or
(B) reduction with sodium borohydride:
A. Catalytic hydrogenation was accomplished in the following
manner. ##SPC7##
In a Paar Pressure Reaction Apparatus were placed 350 mg. (0.0014
mole) of III (purified, M.P. 74.degree. - 77.degree. C.), dissolved
in 25 ml. of methanol and 1 mg. of 10 percent palladium-carbon
catalyst. The reaction was allowed to proceed under 2 - 3 atm. of
hydrogen with mechanical shaking. The reaction was essentially
complete (no aldehyde adsorption at 1675 cm..sup.-.sup.1) after 30
min. After filtering the catalyst the solvent was removed in vacuo
to afford 345 mg. of the diglycidyl ether of 4-methylol resorcinol
IV as a light yellow viscous oil. Analytical thin layer
chromatography revealed a small amount (10 - 15 percent) of the
hydrogenolysis product V had also been formed. A pure sample of IV
(300 mg.) was obtained by preparative thin layer chromatography,
IR, 3500 - 3700 cm..sup.-.sup.1 (OH), 910 cm..sup.-.sup.1
(epoxide); NMR, .tau.CDCl.sub.3 7.5 - 7.0 m. (5H), 6.8 - 6.5 m.
(2H), 5.8 - 4.6 m. (4H), 4.4 br. s. (2H), 3.5 m. (2H), 2.8 m. (1H);
D.sub.2 O/CDCl.sub.3 as above except 7.5 - 7.0 m. (4H), and the
broad, two proton singlet at 4.4 sharpened considerably.
In carrying out the catalytic hydrogenation, care must be taken to
minimize the further reduction of the methylol group to a methyl
group as in compound V. This undesired side reaction can be held to
a minimum by carefully following the reduction with infrared
spectroscopy. It should be noted, however, that a small amount of
the over-reduction product V is not expected to hinder the
reactivity of the resin too much or impair physical properties
since V is still a difunctional epoxy resin.
B. Sodium borohydride is successfully employed to reduce the
carbonyl group without affecting the epoxide group. ##SPC8##
Best results are obtained when sodium borohydride is employed
because most methods of reducing aldehydes result in the opening of
the oxirane ring. In order to reduce the aldehyde group, sodium
borohydride was added slowly to a solution of 20 grams (0.15 mole)
of crude III in 100 ml. of methanol at 5.degree. C., until the
bright yellow color of III disappeared (about 20 min.). The
reaction mixture was then acidified with dilute hydrochloric acid
and extracted several times with chloroform. The combined
chloroform extracts were washed with water and dried over anhydrous
sodium sulfate. The removal of solvent in vacuo afforded crude IV
as a light yellow oil (viscosity--218 stokes). Analytical thin
layer chromatography revealed the product to be 85 - 90 percent IV
in addition to the small amount of higher molecular weight carried
over from the epoxidation step. In either case, crude IV could be
vacuum distilled to give a yellow liquid (viscosity--140 stikes),
B.P. 2 273.degree. C. at 0.6 mm.
The curing of the epoxy monomers of this invention may be
accomplished by the addition of any of the chemical materials known
in the art for curing epoxide resins. Such materials are usually
referred to as curing agents but at times are designated as
activators or catalysts.
Suitable examples of the curing agents which may be employed to
cure the epoxy monomers include those organic nitrogen compounds
that cause the addition polymerization of the epoxy resin molecule.
These curing agents include, various amines, e.g., aliphatic and
aromatic primary and secondary amines, aliphatic and aromatic
polyamines.
Suitable examples of aliphatic and aromatic primary and secondary
amines include diethyleneaminopropylamine, polyamide resins,
dibenzylamine, etc. A particularly preferred aliphatic primary
amine is diethylenetriamine.
The curing agent is employed in at least catalytic amounts, that
is, amounts sufficient to initiate the self-cure of the epoxy resin
monomers of this invention. Generally, the curing agent is used in
amount of from about 10 to about 20 parts by weight and preferably
in a stoichiometric amount based on the weight of the epoxy resin
monomer and the particular curing agent to be employed.
Inert fillers may also be added to the curable compositions of this
invention which comprise the epoxy resin monomer and the curing
agent. These fillers are incorporated into an epoxy resin in order
to reduce the resin content and, more importantly, to reduce the
exothermic heat of reaction. In this regard, it should be noted
that due to the low viscosity of the resins of this invention, a
sufficient amount of fillers may be incorporated into the cured
resins of this invention to reduce the exothermic heat of reaction,
thus enabling the resins of this invention to be used as adhesives,
protective coatings and/or encapsulants for heat-sensitive
electrical components. Examples of suitable fillers include sand,
crushed shells, rocks, aluminum powder, steel powder, iron
particles, quartz powder, titanium dioxide, asbestos, silica,
calcium carbonate, graphite, black iron oxide, silicon dioxide,
diatomaceous earth and the like. A particularly preferred filler is
silica. The relative proportion of filler employed in the curable
compositions of this invention may vary from 0 to about 50 percent
by weight of the epoxy resin monomer depending upon the particle
size of the filler and the desired viscosity of the filled
resin.
Preliminary tests indicate that the diglycidyl ether of 4-methylol
resorcinol reacts more rapidly at room temperature than similar
high molecular weight resins and is less viscous when purified. The
results of these tests are summarized in Table 1, below.
In carrying out these tests, the rate of disappearance of the
epoxide function during curing was easily followed by infrared
spectroscopy. This was done most readily by periodically observing
the decrease in intensity of the characteristic epoxide adsorption
band at 910 cm..sup.-.sup.1 Measurements were taken on a thin layer
sample spread between two sodium chloride plates, thus excluding
effects on the relative rates due to exotherms. Cure was considered
complete at a given temperature when no further decrease in
intensity of the absorption band could be observed.
In order to determine the relative reactivity of the new resin, the
diglycidyl ether of 4-methylol resorcinol (IV) was cured with
diethylenetriamine (DETA). This cure rate was compared with:
A. A standard bisphenol A-type resin of the formula: ##SPC9##
B. A modified bisphenol A resin with a methylol group proximate to
an oxirane ring of the formula: ##SPC10##
C. A standard resorcinol resin of the formula: ##SPC11##
D. And the diglycidyl ether of .beta.-resorcylaldehyde (Formula
III).
All the resins were cured with DETA and the amount of DETA used in
each case was adjusted to compensate for differences in the epoxide
equivalents in each resin. All runs were made at room temperature
(25.degree. C.).
The viscosity of each of the above resins was determined at room
temperature with a series of Gardner Bubble Viscosity Tubes. A
sample of the resin was introduced into a standard sample tube
until the size of the bubble trapped air approximated that of the
reference tubes. The tubes containing the samples and the reference
liquids were inverted and the sample was matched to a reference
liquid that had the same bubble rise times. If the sample viscosity
lay between the viscosities of the two reference liquids, the
bubble rise time was recorded for all three, and the viscosity of
the sample calculated accordingly. In this manner the viscosity of
each of the resins was determined and is recorded in Table I,
below.
By referring to Table I, below, the preliminary tests show that the
diglycidyl ether of 4-methylol resorcinol reacts more rapidly with
primary amine curing agents than all currently available resins
while still offering flexibility in formulating resin compositions.
The tests show that resin IV reacts about 50 times faster than
standard bisphenol A-type resin VI, 5 times faster than standard
resorcinol based resin VIII, and 2 - 3 times faster than modified
bisphenol A-type resin VII. The gelling within 7 minutes of thin
sections of the intermediate diglycidyl ether of
.beta.-resorcylaldehyde (III) was due to the initial reaction of
DETA with the carbonyl function along with some concurrent
crosslinking through the epoxide functions. Upon mild heating
(about 100.degree. C.) the infrared spectrun revealed that the
epoxide band at 910 cm..sup.-.sup.1 had completely disappeared and
that a new band had appeared at 1670 cm..sup.-.sup.1 (imine
absorption, --C=N--). These observations are consistent with the
following mechanism following Table I for the reaction of the
aldehyde moiety:
TABLE I
__________________________________________________________________________
CURE RATES AND VISCOSITIES OF EPOXY RESINS Phr. DETA curing
Viscosity in Cure time Resin agent stokes (by infrared)
__________________________________________________________________________
Diglycidyl ether of 4- 16.8 218 (crude) 35 minutes methylol
resorcinol (IV). 140 (distilled) Modified bisphenol A (VII) 9.7
196-2,000 75 minutes solid..sup.2 Standard bisphenol A (VI) 11 142
25 hours..sup.b Standard resorcinol (VIII) 15 3-4c 135 minutes
Diglycidyl ether of .beta.-resor- 20 9c 7 minutes..sup.d
cylaldehyde (III).
__________________________________________________________________________
.sup.a Initial samples of this resin were essentially solid,
showing no flow at room temperature. A sample of an improved resin
(reported to have the higher homologs removed) had a viscosity of
about 190 stokes. A third sample, supposedly the same improved
resin (was extremely viscous, possessing a viscosity of over 2,000
stokes. .sup.b Additional heating at 75.degree. C. for 1 hr. needed
for complete cure. .sup.c Being pure, high monomer content epoxy
resins III and VIII are subject to crystalization upon standing at
room temperature. Gentle heating at 60.degree. C. is sufficient to
reliquify the resins. .sup.d Heating at 108.degree. C. for 0.5 hr.
needed for complete disappearance of epoxide absorption at 910
cm..sup.-.sup.1 in the infrare spectrum. Aldehyde absorption at
1,675 cm..sup.-.sup.1 had disappeared after 7 minutes.
##SPC12##
It should be understood that the invention is not limited to the
exact details of construction shown and described herein for
obvious modifications will occur to persons skilled in the art.
Accordingly,
* * * * *